Because of constraints in forming the daughter fission-product nuclei, spontaneous fission into known nuclides becomes theoretically possible (that is, energetically possible) for some atomic nuclei with atomic masses greater than 92 atomic mass units (amu), with the probability of spontaneous fission increasing as the atomic mass increases above this value.

Chart of nuclides (isotopes) depicting the valley of stability by type of decay. The diagonal line corresponds to equal numbers of neutrons and protons. Black squares are stable nuclides. Elements with more than 20 protons must have an increasing number of neutrons than protons to be stable. Nuclides with excessive neutrons or protons are unstable and prone to β− (teal) or β+ (pink) decay, respectively. Spontaneous fission decays (SF, green) occur only for nuclides in the far upper right, that is nuclides with high atomic and neutron numbers.

The lightest natural nuclides that are hypothetically subject to spontaneous fission are niobium-93 and molybdenum-94 (elements 41 and 42, respectively)[verification needed]. Spontaneous fission has never been observed in the naturally occurring isotopes of these elements, however. In practice, these are stable isotopes.

Spontaneous fission is feasible over practical observation times only for atomic masses of 232 amu or more. These are elements at least as heavy as thorium-232 – which has a half-life somewhat longer than the age of the universe. Thorium-232 is the lightest primordial nuclide that has left evidence of undergoing spontaneous fission in its minerals.

The known elements most susceptible to spontaneous fission are the synthetic high-atomic-number actinides and transactinides with atomic numbers from 100 onwards.

For naturally occurring thorium, uranium-235, and uranium-238, spontaneous fission does occur rarely, but in the vast majority of the radioactive decay of these atoms, alpha decay or beta decay occurs instead. Hence, the spontaneous fission of these isotopes is usually negligible, except in using the exact branching ratios when finding the radioactivity of a sample of these elements.

In practice 239Pu will invariably contain a certain amount of 240Pu due to the tendency of 239Pu to absorb an additional neutron during production. 240Pu's high rate of spontaneous fission events makes it an undesirable contaminant. Weapons-grade plutonium contains no more than 7.0% 240Pu.

Spontaneous fission gives much the same result as induced nuclear fission. However, like other forms of radioactive decay, it occurs due to quantum tunneling, without the atom having been struck by a neutron or other particle as in induced nuclear fission. Spontaneous fissions release neutrons as all fissions do, so if a critical mass is present, a spontaneous fission can initiate a self-sustaining chain reaction. Radioisotopes for which spontaneous fission is not negligible can be used as neutron sources. For example, californium-252 (half-life 2.645 years, SF branch ratio about 3.1 percent) can be used for this purpose. The neutrons released can be used to inspect airline luggage for hidden explosives, to gauge the moisture content of soil in highway and building construction, or to measure the moisture of materials stored in silos, for example.

As long as the spontaneous fission gives a negligible reduction of the number of nuclei that can undergo such fission, this process can be approximated closely as a Poisson process. In this situation, for short time intervals the probability of a spontaneous fission is directly proportional to the length of time.

The spontaneous fission of uranium-238 and uranium-235 does leave trails of damage in the crystal structure of uranium-containing minerals when the fission fragments recoil through them. These trails, or fission tracks, are the foundation of the radiometric dating method called fission track dating.